WO2019111268A1 - Procédé de quantification sélective et sensible de sulfure d'hydrogène - Google Patents

Procédé de quantification sélective et sensible de sulfure d'hydrogène Download PDF

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Publication number
WO2019111268A1
WO2019111268A1 PCT/IN2018/000055 IN2018000055W WO2019111268A1 WO 2019111268 A1 WO2019111268 A1 WO 2019111268A1 IN 2018000055 W IN2018000055 W IN 2018000055W WO 2019111268 A1 WO2019111268 A1 WO 2019111268A1
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WIPO (PCT)
Prior art keywords
hydrogen sulfide
selective
quantification
sulfide
dye
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PCT/IN2018/000055
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English (en)
Inventor
K. M. Muraleedharan
K Ramshad
C Lakshmi
T.t DIVYA
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INDIAN INSTITUTE OF TECHNOLOGY MADRAS (IIT Madras)
National Institute Of Technology Calicut
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Application filed by INDIAN INSTITUTE OF TECHNOLOGY MADRAS (IIT Madras), National Institute Of Technology Calicut filed Critical INDIAN INSTITUTE OF TECHNOLOGY MADRAS (IIT Madras)
Publication of WO2019111268A1 publication Critical patent/WO2019111268A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/223—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
    • G01N31/224—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols for investigating presence of dangerous gases

Definitions

  • Embodiments are generally related to the field of analytical chemistry. Embodiments are further related to methods for selective detection and quantification of hydrogen sulfide (H 2 S) in biological samples or samples of environmental/industrial origin using triarylmethane dyes. Embodiments are furthermore related to detection and management of clinical conditions, including, but not limited to, sepsis and quantification of hydrogen sulfide in other environmental or industrial samples. Embodiments are more particularly related to methods for selective and sensitive quantification of hydrogen sulfide (H 2 S) using new triaryl methane dyes.
  • Hydrogen sulfide is generally known for its foul smell and has recently been identified as a gasotrasmitter that regulates a number of physiological and pathological processes. It is one of the endogenous gasotransmitters like nitric oxide (E. Culotta et al. , Science, 1992, 258, 1862) and carbon monoxide (S.
  • CBS cystathionine-p-synthase
  • Sepsis is a clinical condition in which the body’s reactions to microbial infection become uncontrolled, which in turn damages various organs.
  • Clinical studies have shown that H 2 S levels are elevated under Sepsis condition and therefore levels of H 2 S can be used as a marker for monitoring the inflammatory reposes or the onset of Sepsis.
  • Hydrogen sulfide is present in human blood in the concentration range of 10-100 mM (J. Chang et al., Curr. Opin. Chem. Biol., 2012 , 16, 595) and up to 600 mM in the brain (Z. Guo et al, Angew. Chem., Int. Ed., 2013, 52, 1688). Therefore, H 2 S probes for biological applications should be able to respond to H 2 S in the micro molar range. However there are only a few probes like Danzyl azide which satisfy this requirement (B. Wang et al., Angew. Chem. Int.
  • Rhodamine based probes have a wider concentration range for detection compared to other probes but requires more response time (10-600 mM; C. J. Chang et al., J. Am. Chem. Soc., 2011, 133, 10078).
  • the reaction takes more than 60 minutes for completion and only a 7 - fold enhancement in fluorescence is observed.
  • Real-time analysis is possible only when the probe changes its photo- physical properties rapidly.
  • Majority of prior art probes which use reducing power of H 2 S or its nucleophilicity (other than sulfonyl azide derivatives) take longer duration (more than 30 minutes) to respond. (B. Wang et al, J. Fluoresc., 2014, 24, 1).
  • sulfonylderivarives such as, dansyl azide
  • the emission intensity of the reduction product in this case is known to get enhanced upon binding with plasma proteins, which could bring error during H 2 S quantifications.
  • the signal output is faster in the case of metal displacement method (S. Wang et al, Analytica Chimica Acta , 2015, 879, 104) like CuS precipitation (J. Chang et al., Curr. Opin. Chem. Biol., 2012, 16, 595).
  • this method is less selective compared to reaction-based probes.
  • the prior arts probes are unable to satisfy the requirements for continuous monitoring of H 2 S with short detection time, high sensitivity, high selectivity, good chemical stability, water solubility and noninterference from other bio-molecules in the photo-physical output.
  • one aspect of the disclosed embodiment is to provide method for selective detection and quantification of hydrogen sulfide in samples of biological origin such as blood plasma.
  • Another aspect of the disclosed embodiment is to provide a method for selective detection and quantification of hydrogen sulfide in samples of environmental origins including oils, etc.
  • Further aspect of the disclosed embodiment is to provide method for selective and sensitive quantification of hydrogen sulfide (H2S) using new triaryl methane dyes.
  • a method for selective and sensitive quantification of hydrogen sulfide (H 2 S) using new triaryl methane dyes is disclosed herein.
  • the proposed method involves a two-step protocol in which addition of this nucleophile to the dye leads to initial loss of its characteristic absorption. Since this addition step cannot discriminate ions such as, hydrogen sulfide, sulfite, thiosulfate etc.,., a second metal salt-mediated de-sulfiiration step is adapted where selective regeneration of the original dye from its hydrogen sulfide (H 2 S) adduct is allowed, which can be detected and quantified.
  • the proposed method takes very shorter time period (less than a minute altogether) therefore effective and useful in continuous monitoring of H 2 S levels in different types of samples mentioned above.
  • the proposed invention pertains to the development of triarylmethane dyes (malachite green derivatives) for the selective detection and quantification of hydrogen sulfide in different types of analytes such as, for example, but not limited to, biological samples, samples of environmental origins such as oils, gases etc.
  • the proposed method can be effectively adapted for monitoring of H 2 S levels in patients with Sepsis and could significantly help in the early detection and management of severe inflammatory responses.
  • the proposed method may be effectively employed for detection and monitoring of H 2 S in industrial processes such as for example, but not limited to, oil and coal fields, and handle health-and environmental issues.
  • the proposed method uses nucleophilicity of H 2 S or its other ionic forms like HS or S (here referred as sulfide) which on addition to malachite green derivatives (such as, tri aryl methane dyes) cause a change in their photophysical properties.
  • the selective detection of such sulfide can be achieved by including a second step in which the dye-H 2 S adduct was made to react with metal salts (ZnCl 2 , CdCl 2 etc). This regenerates the parent dye with precipitation of corresponding metal sulfide. Since the regeneration step is highly selective for sulfide, the recovery of photo-physical signal can be quantitatively correlated with sulfide concentration.
  • the first step is instantaneous and the second metal- mediated dye regeneration require only about 50 seconds. Thus the detection and quantification can be completed in a minute to achieve fastest results of the method.
  • FIG. 1 illustrates a schematic representation of a method for selective detection and quantification of hydrogen sulfide (H 2 S) using triarylmethane dyes, in accordance with the disclosed embodiments;
  • FIG. 2 illustrates a graphical representation illustrating the concentration of Sodium Sulfite, in accordance with the disclosed embodiments.
  • FIG. 1 illustrates a schematic representation 100 of a method for selective detection and quantification of hydrogen sulfide (H 2 S) in samples of biological or environmental origin using triarylmethane dyes, in accordance with the disclosed embodiments.
  • the proposed method involves a two-step protocol in which the nucleophile is added to malachite green derivatives which lead to initial loss of its characteristic absorption. Note that this addition step do not discriminate ions such as, hydrogen sulfide, sulfite, thiosulfate etc.
  • a second metal salt-mediated de-sulfuration step is adapted where selective regeneration of the original dye from its hydrogen sulfide (H2S) adduct is allowed, which can be detected and quantified.
  • H2S hydrogen sulfide
  • the proposed method takes very shorter time period (less than a minute) therefore effective and useful in continuous monitoring of H 2 S levels in samples of biological and environmental origin.
  • Malachite green is a well-known compound in the area of dye chemistry. It has good absorption at 618 nm and has very good affinity towards nucleophilic compounds like sulfite, H 2 S and thiosulfate. Absorbance of malachite green gets abolished in the presence of these nucleophiles due to adduct formation (F. Colmenero et.al., Food Additives and Contaminants , 2008, 25, 1167). Apart from its use in dye industry, it is generally known as a sensor for sulfiite and is used for the removal of sulfite from aquatic medium. Major emphasis of research has been on sulfite ion detection since it is a well-known food additive (C. Francisco et. al.,
  • the proposed invention pertains to the development of malachite green derivatives for the selective detection and quantification of hydrogen sulfide in different types of analytes such as, for example, but not limited to, biological samples, those of environmental origins and mammalian samples.
  • the proposed method can be effectively adapted for monitoring of H 2 S levels in patients with Sepsis and can significantly help in the early detection and management of severe inflammatory responses.
  • the proposed method can be effectively employed for detection and safe handling of H 2 S in industrial applications such as for example, but not limited to, oil and coal fields, and handle health-and environmental impacts.
  • nitro-derivative 14b The response from nitro-derivative 14b is nearly 15 times better than that of malachite green. Note that the scope of the proposed method is not however limited to 14 b, and any derivative in this series with one or more electron- withdrawing groups like CN, CF 3 , N0 2 etc. on one or more of the aromatic rings with good balance of reactivity may be considered.
  • the proposed method uses nucleophilicity of H 2 S which on addition to malachite green derivatives (such as, triarylmethane dyes) cause a change in their photo-physical properties.
  • the selective detection of H 2 S can be achieved by including a second step in which the dye-H 2 S adduct was made to react with metal salts like ZnCl 2 , CdCl 2 etc. This is not however limited to these salts but others which also promote desulfuration and regenerate the dye may also be considered.
  • the second step thus regenerates the parent dye with precipitation of corresponding metal sulfide. Since the regeneration step is highly selective for sulfide, the recovery of photo-physical signal can be quantitatively correlated with sulfide concentration.
  • the first step is instantaneous and the second metal mediated dye regeneration require only about 50 seconds. Thus the detection and quantification can be completed in a minute to achieve fastest results of the method.
  • FIG. 2 illustrates a graphical representation 200 of the change in absorbance in samples containing mixture of sulfite and sulfide when they are subjected to the present method for H 2 S estimation.
  • These set of experiments involving mixture of H 2 S and sulfite ions were conducted to estimate the concentration of sulfide accurately in presence an interfering ion like Sulfite.
  • the concentrations of the probe and H 2 S in all the samples were kept constant (40 mM and 50 mM respectively) and that of sulfite ions were varied systematically from 0-50 mM.
  • the first step should show a reduction in absorbance of 14b due to reactions involving both H 2 S and the sulfite, but the regeneration step should be specific for only H 2 S-adduct. Since the concentration of H 2 S used was same in all the experiments, the gain in absorbance on treatment with the metal salt should remain the same in all cases. As shown in FIG. 2, the first step indicated a progressive reduction of absorbance due to combined effects from both ions. However, on treatment with 200 mM CdCl 2 solution (second step), the regenerated absorbance remained the same as expected.
  • the FIG. 2 given below depicts the absorbance values after step 1 and step 2 for each of the sulfite concentrations.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Biophysics (AREA)
  • Molecular Biology (AREA)
  • Physics & Mathematics (AREA)
  • Toxicology (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

L'invention concerne un procédé de quantification sélective et sensible de sulfure d'hydrogène (H2S) à l'aide de nouveaux colorants triarylméthaniques. Le procédé de l'invention comprend un protocole à deux étapes selon lequel le nucléophile est ajouté à des dérivés verts de malachite, ce qui conduit à une perte ou une diminution initiale de son absorption caractéristique. Ensuite, une seconde étape de désulfuration à médiation par un sel métallique est adaptée là où une régénération sélective du colorant d'origine à partir de son produit d'addition de sulfure d'hydrogène (H2S) est autorisée, ce dernier pouvant être détecté et quantifié. Le procédé de l'invention prend une durée très courte (moins d'une minute), il est donc efficace et une utile dans la surveillance continue de niveaux de H2S dans des échantillons biologiques et de mammifères.
PCT/IN2018/000055 2017-12-05 2018-12-03 Procédé de quantification sélective et sensible de sulfure d'hydrogène WO2019111268A1 (fr)

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IN201741043637 2017-12-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024006923A3 (fr) * 2022-06-30 2024-02-08 The Cleveland Clinic Foundation Quantification totale de sulfure d'hydrogène

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623613A (en) * 1984-12-25 1986-11-18 Konishiroku Photo Industry Co., Ltd. Method of processing light-sensitive silver halide photographic material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4623613A (en) * 1984-12-25 1986-11-18 Konishiroku Photo Industry Co., Ltd. Method of processing light-sensitive silver halide photographic material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ABBAS AFKHAMI ET AL., SIMULTANEOUS KINETIC SPECTROPHOTOMETRIC DETERMINATION OF SULFITE AND SULFIDE USING PARTIAL LEAST SQUARES (PLS) REGRESSION, 12 January 2006 (2006-01-12) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024006923A3 (fr) * 2022-06-30 2024-02-08 The Cleveland Clinic Foundation Quantification totale de sulfure d'hydrogène

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